CA1116784A - Process for the preparation of polyvinylbutyral having improved properties - Google Patents
Process for the preparation of polyvinylbutyral having improved propertiesInfo
- Publication number
- CA1116784A CA1116784A CA000307711A CA307711A CA1116784A CA 1116784 A CA1116784 A CA 1116784A CA 000307711 A CA000307711 A CA 000307711A CA 307711 A CA307711 A CA 307711A CA 1116784 A CA1116784 A CA 1116784A
- Authority
- CA
- Canada
- Prior art keywords
- polyvinylbutyral
- weight
- treatment
- polymer
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/48—Isomerisation; Cyclisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31627—Next to aldehyde or ketone condensation product
- Y10T428/3163—Next to acetal of polymerized unsaturated alcohol [e.g., formal butyral, etc.]
Abstract
PROCESS FOR THE PREPARATION OF POLYVINYLBUTYRAL HAVING
IMPROVED PROPERTIES
Abstract of the disclosure:
The preparation of polyvinylbutyral is commonly effect-ed by the acetalization of polyvinyl alcohol with n-butyr-aldehyde, either in an organic solvent or in water. By varying the reaction conditions it is possible to obtain the polyvinylbutyral in a coarse-grain or fine-grained form. The production of polyvinylbutyral having improved properties is possible by using a polyvinylbutyral having a content of from 17 to 24 % by weight of vinyl alcohol units as starting material for an after-treatment in the presence of an organic sulfonic acid having an emulsifying effect. The polyvinylbutyral obtained is particularly suitable for the manufacture of compound sheets.
IMPROVED PROPERTIES
Abstract of the disclosure:
The preparation of polyvinylbutyral is commonly effect-ed by the acetalization of polyvinyl alcohol with n-butyr-aldehyde, either in an organic solvent or in water. By varying the reaction conditions it is possible to obtain the polyvinylbutyral in a coarse-grain or fine-grained form. The production of polyvinylbutyral having improved properties is possible by using a polyvinylbutyral having a content of from 17 to 24 % by weight of vinyl alcohol units as starting material for an after-treatment in the presence of an organic sulfonic acid having an emulsifying effect. The polyvinylbutyral obtained is particularly suitable for the manufacture of compound sheets.
Description
- 2 - HOE 77/F 14Q
The present invention relates to a process for tne pre-paration of poly~inylbutyral having improved properties.
It has already been suggested to prepare polyvinyl~uty-ral by acetalization OL polyvinyl alcohol with n-butyral. According to one of the processes common intechnology, polyvinyl alcohol is dispersed in an orga-nic solvent, for exam?le ethanol, and reacted in the pre-sence of an acid with butyraldehyde. As a result, a solu-tion of high-quality polyvinylbutyral is obtained. HOW-1~ ever, the drawbacks of this process are to be seen in thecomplicated isolation of the polymer from the solution and in the recovery of the solvent.
There have therefore been numerous attempts to re~ot polyvinyl alcohol in an aqueous solution to give polyvi--nylbutyral, in which prooess the polymer precipitatesfrom the solution and may be separated by filtration. By this proce~s it is difficult to prepare a polymar grain of a hieh uniformity which can easily be filterd. For example, an aqueous polyvinyl alcohol solution can be reacted at a temperature of from 50 to 100C with butyraldehyde in the presence of an acid, with the addition of from 0.04 to 0 2 ~ of an emulsifier after starting the reaction (cf.
German Patent Specification No. 1 247 663). In spite of an intensive mechanical agitation of the react.ion mixture the polyme~ is relatively coarse-grained and not uniform, ~o that the ~ubsequent proces3ing, for example in the presence of plasticizers to give sheets, involves some difficult es.
2g - It has 4urther been suggQs~ed to start the acetal-z~
71~
The present invention relates to a process for tne pre-paration of poly~inylbutyral having improved properties.
It has already been suggested to prepare polyvinyl~uty-ral by acetalization OL polyvinyl alcohol with n-butyral. According to one of the processes common intechnology, polyvinyl alcohol is dispersed in an orga-nic solvent, for exam?le ethanol, and reacted in the pre-sence of an acid with butyraldehyde. As a result, a solu-tion of high-quality polyvinylbutyral is obtained. HOW-1~ ever, the drawbacks of this process are to be seen in thecomplicated isolation of the polymer from the solution and in the recovery of the solvent.
There have therefore been numerous attempts to re~ot polyvinyl alcohol in an aqueous solution to give polyvi--nylbutyral, in which prooess the polymer precipitatesfrom the solution and may be separated by filtration. By this proce~s it is difficult to prepare a polymar grain of a hieh uniformity which can easily be filterd. For example, an aqueous polyvinyl alcohol solution can be reacted at a temperature of from 50 to 100C with butyraldehyde in the presence of an acid, with the addition of from 0.04 to 0 2 ~ of an emulsifier after starting the reaction (cf.
German Patent Specification No. 1 247 663). In spite of an intensive mechanical agitation of the react.ion mixture the polyme~ is relatively coarse-grained and not uniform, ~o that the ~ubsequent proces3ing, for example in the presence of plasticizers to give sheets, involves some difficult es.
2g - It has 4urther been suggQs~ed to start the acetal-z~
71~
- 3 - HOE 77~F 140 tion at a t_n;pelature of less than 20C (cf. German ?ater.t Specification ~o. 9011 592). In the course of this process the polymer precipitates after some time in the form of fine particles. In its further progress, the reaction may be accelerated by an increase in temeprature, without changing the favorable filtering properties and the high uniformity of the polymer. However, several properties which are important for the processing of the polymer are unsatisfactory, for example the strength and stickiness.
Finally, there has also been suggested a process for the preparation of polyvinylacetals in which process a polyvinyl alcohol is condensed with an aldehyde in an aqueuos phase and in the presence of an acid catalyst (cf.
German Offenlegungsschrift No. 2 365 005). In the course of this process the reaction mixture is maintained at a temperature of 20C at the most, in order to let the reaction product precipitate, and subsequently the react ion is continued at a temperature of at least 30C.
The above-rr.entioned processes are characterized by the common feature that the reaction is discontinued as soon as the desired degree of acetalization is reached. In this process it is frequently put up with the fact that the acetali2ation equilibrium has not yet been reached, i.e. the reaction is carried out with an excess amount of butyraldehyde and is discontinued prior to reaching the acetalization equilibrium.
The present inYention relates to a process for the preparaticn of polyvinylbutyral ha-ving improveà proper~
29 tiès and comprises sub~ecting a polyvinylbutvral having _ 4 _ HOE 77/F 140 a ViSCO~lty o~ frcm lO to 200 cp (measured according to DiN 53 015 ar a 5 ~ by weight s.lution in etnanol at 23C) and a content of from 17 to 24 ~ by weight of ~inyl alcohol units n an aqueous medium, at a temperatu~e of 50 to 70~C in the presence o~ from 0.01 t~,5 % by weight, - calculated on the polyvinylbutyral, of an organic sulfonic acid being e~ecti-~re as emulsifier and having from 8 to 30 carbon atoms to ar. after-treatment Ior 0.5 to 10 hours under acetalization conditions knot~l per se, and thereafter separating said poiyvinylbutyral as usual.
The polyvinylbutyral obtained according to the inven-tion is marked by a considerably increased strength and stiffness and at the same time shows a reduced solubility.
For the process Or the invention it is, in principle, insi~nificant according to ~rhich process the polyvinylbu-tyral employed has been prepared. ~lowever, since the after-treatment is effected in an aqueous phase, it is advanta~eou~ to use polyvi.nylbutyrals which have also been prepared in a~ aqueous ph~se. For this process it is particularly ad~antageous to effect the after-treatment immediately and without interruption following the acetalization, so that the acetalization and the after-treatment are carried out in a single operation without separating the acetalization liquor, and the reaction product is subse~uently separated in known manner.
However, also dry polyvinylbutyrai powder may be subjected to the a~ter-treatment o~ the in~ention.
The a~ter~treatment Ol a poly-~inylbutyral prepared in 29 an aqueous pha~e, in -~hose pleparatiorl the reaction tem ~ 5 ~ _ 7~F 140 perature nas ~e~ less than 20C up to the co~pletion o~
the acetallzation~ is particularly advantageous. This means that in this case the polyvinylbutyral is obtained in a grain size (particle diameter) which is less than 1 millimet2r for more than 90 %, for the most part even less than 0.5 millimeter, and which is therefore particularly suitable for the after-treatment. In the case of coarser polyvinylb~tyral particles it is recommended to grind the particles to the grain size indicated prior to the after-treatment.
The improvement of the mechanical properties dependsonly to a minor degree on the molecular weight of the polyvinylbutyral employed. It is therefore possible to subject polyvinylbutyrals of a range of molecu].ar weight which is as extensive as is interesting in practice to the after-treatlnent according to the invention. In this range there are generally polyvinylbutyrals having a viscosity of from 10 to 200 cp, preferably from 50 to 100 cp (measur-ed according to DIN 53 015 at a 5 % by wei~ht solution in ethanol at 23C).
Of special importance for the success of the process according to the invention is the chemical composition of the polyvinylbutyral. In principle, it is easier to im-prove the ~echanical properties in polyvinylbutyrals which have a high content of vinyl alcohol units than in those having a lo-.~ content of vinyl alcohol units. If the portion of vinyl alcohol units is les~ than 17 ~ by weight, a distinct improvement of the mechanical properties can no 29 longer be observed. If the portion is more than 24 ~ ~y 73 ~
- 6 - HOE 7'1/F 140 weightJ tn~ a~ter-Lreatment yields a polyvinylbutyral which can no longer be processed satisfactorily. This i5 why there is used a polyvinylbutyral having a content of from 17 ~o 24 ~ bv weight and preferably from 18 to 23 ~ by weight of vinyl alcohol units.
The mechanical properties of the reaction ~roduct are al50 strongly influenced by the temperature applied in the after-treatment. Temperatures of less ihan 50C are not recommended, since the reaction will take too long in this case. At a temperature of more than 65C, in the case of high molecular weight polyvinylbutyrals of more than 70C, the polymer shows a tendency to-:ard.s a larger grain size and lump f`ormation. The process is therefore oarried out generally at a temperature in the range of from 50 to 70~, preferably 50 to 65C.
The period of after-treatment is generally in the range of from 0.~ to 10 hours, preferably from 1 to 7 hours.
A particularly important requirement for improving the proper~ies of the polyvinylbutyral ~y the after-treat-ment according to the invention is the presence of from 0.01 to 0.5, preferably from 0.05 to 0.2 p by weight, cal-culated on the polyvinylbutyral, of an organic sulfonic acid having from 8 to 30 carbon atoms and bein~ effective as emulsifier. There are suitable for this purpose alkyl~
sulfonic acid~ and alkyiaryl-sulfonic acids, for example dodecylben~ene-sulfonic acid or he~adecane~sulfonic ac.id.
It is also ?ossible to use r.~i~tures of such acids. The 29 aliphatic radical of the sulfonic acifls may be br2nclled - 7 - HOF._77/F 140 and the aro~atic radical may a~so be substituted by one or several alkyl grou?s.
The after-treatment is generally carried out in an aqueous medium under usual acetalization conditions, while using from I to 100 parts by weight of water per part by weight of polymer and from about 0.1 to 5 % by weight of an inorganic acid, calculated on the aqueous medium. The reaction mixture is normally agitated by stirring. As inorganic acid there is used preferably sulfuric acid or hydrochloric acid. Further it is recommended, in order ro maintain the existing degree of acetalization in the poly-mer, to add n~butyraldehyde in an amount approxima-tely corresponding to the equilibrium concentration, for which purpose from 0.1 to 5 ~ by weight, calculated on the polymer, are sufficient, depending on the reaction condi-tions. The concentration of n-butyraldehyde is to be chosen in such a manner that the portion of vinyl alcohol units is in the range of from 17 to 2l~, prefcrably from 18 to 23 % by weight, also in the after-treated polymer.
2Q Due to the described addition ol an excess amount of inorganic acid it is not absolutely necessary t~ employ the organic sulfonic acid having an emulsifying effect as free acid. ~ather, use may be made also of any salts of these sulfonic acids, from which the free acid is formed in the raction mixture.
The after-treatment of the poly~inylbutyral accord-ing to the inventlon is completed by the separation of the final product. This proces$ i3 carried out ln the same 2~ manner as ~nown for the prepararion of pol-yvinyl~utyrals - 8 - HOE 77/F 1Ll0 from arl a~ue~us In~^iiurn. The ~orking-up consists in the complete remo~al of the acid from the polymer, preferably by a thorough washin~ with water. According to known methods it is recommendeA to apply a small amount of alkali onto the polymer Drior to the subsequent drying, so that from 5 to 100 ml of 0.01 normal HCl solution are requiredS for example, to neutralize 100 g of polyvinyl-butyral.
It is a special advantage of the process of the in-vention that the properties of the final pro-duct can be influenced gradually and in a reproducible manner by vary~
ing the individual process features. This is particularly important, since the structure of the polyvinylbutyral employed as starting material may be variable depending on the conditions of its prepar-tion. Polyvinylbutyrals which have been prepared, for example, at a low temperature, have a structure whi^h is as a rule more statistic than that of pol.yvinylbutyrals obtained at hi~;her temperatures. There-fore it is possible to obtain from the former throu~h an intensive after-treatment a final product of the same qua-lity as that of the latter products which are not modi-fied as strongly by the conditions of the after-treatment.
The manner in which the properties of the polyvinyl-butyral are influenced through a modification of the pro-~5 cess parameters during the after-treatment according to the invention can be ascertained without difficulty, for example, by determining the ~iscosity of a 5 % ethanolic so]ution at 23C aceording to DIN 53 015 and observing the 29 ~:iscosity change at this tem.?erature.
- 9 - H0~_77/F 140 For t~1ls ~ut~posc the polyvinylbutyral is dissolved at 70(. Sui)sequently the soluti.on is cooled wit.hin 5 minutes to the measuring temperature, and the viscosity is determir.ed immedi.ately. Following definite periods of time r for example after one hour, one day and~or one week each, the viscosity is again determined at 23C. Those polymers having ~ portion of vinyl alcohol units of less than 23 ~ by weight which have not been after-treated do practicaliy not sho~ any change of viscosity in this treatment. Polyvinylbutyrals which have been after--treated for only a short time show only a slight thickening in solution, whereas those polyvinylbutyrals which have been after-treated for several hours under more strict condi-tions, for example at a temperature of more than 65C and in the presence of more than 0.2 ~ by weight of alkane-sulfonic acid, may thicken in solution already within one hour.
In principle, it is also possible, however, to ob-serve the chang~ of the properties of the polyvinyl~utyral by measuring all the other properties that are altered by the after-treatment.
The property changes of the polyvinylbutyral obtain-ed by the process according to the invention are very con-spicuous. Especially the strength and the stiffness of the polymer are increased considerably. Plasticized sheets which are prepared from the polyvinylbutyral treated ac cor~in~Y to the inventioll show a stiffness that has been marked~y încreased, a stren~th that has been considera`nly 29 increased 2t a defined elongati.on, as well as an increaced ~ '7~
tensile strnngth with an elongation at tear only sli~htly reduced, as compared with known Doiyvinylbutyral sheets.
At a temperature Or less than 100C the sheets manufac-tured from the polyvinylbuty!al prepared according to the invention show a tendency to flowing that has been consi-derably reduced, which facilitates their use as oonding sheets for sa~ety glass. Further the after-treatment ac-cording to the invention surprisingly also strongly re-duces the undesired stickiness of the polyvinylbutyral sheets. When using polyvinylbutyral having an appropriate molecular weight distribution, the flow and the processing properties are in no way adversely affected as compared with known polyvinylbutyrals. In spite of the reduced solubility of the polyvinylbutyral in some solvents, which t5 ls caused by the after-treatment, said polyvinylbutyral is excellently compatible with common plasticizers and yields sheets having a high transparency.
The p.ocessing of the polyvinylbutyral obtained by thc after-treatment according to the invention into bond-ing sheets is carried out in usual manner. As the flowproperties in the plasticizer-containing melt are reduced by the after-treatment, it is recommended to employ poly-mers having a molecular weight - expressed by the viscosity in a 5 ~ ethanolic solution at 23C according to DIN
53 015 - which is generally lower than with the polyvinyl-butyrals commonly used for this purpose. In order to further i~prove the flow properties it is also possible to add polyvinylbutyrals having a lower molecular weight.
29 Finally, the proce3sing properties of the polyvinylbutyral 3~
prepared il7 accord-~nce with the invention may also be influenced '~y varying the plastici~er added.
The amount of plasticizer to be added is generally in the range of from 20 to 60 parts by .~eight, especially from 30 to 50 parts by weight for 100 parts by weight of polyvinylbutyral. As plasticizers there are used the compounds th~t are commonly employed, especially esters of polyhydric alcohols or of polybasic acids. There are suitable, for example, esters of triethylene-glycol with aliphatic carboxylic acids havj.ng from 6 to 10 carbon atoms, such as, in particular, 2-ethylbutyric acid, gly-cerol monooleate, dibutyl sebacate, di(B-butoxymethyl)-adipate, dioctylphthalate and tricresyl phosphate. These plasticizers may be used individually or combined.
Furthermore, there may be added a substance which makes the mixture stable to degr~dation, for example, a small ~mount of an alkali or a ~alt having an alkaline reaction, moreover, an oxidation stabilizer, such as a phenol, bisphenol or terpene phenol substituted in the 2,
Finally, there has also been suggested a process for the preparation of polyvinylacetals in which process a polyvinyl alcohol is condensed with an aldehyde in an aqueuos phase and in the presence of an acid catalyst (cf.
German Offenlegungsschrift No. 2 365 005). In the course of this process the reaction mixture is maintained at a temperature of 20C at the most, in order to let the reaction product precipitate, and subsequently the react ion is continued at a temperature of at least 30C.
The above-rr.entioned processes are characterized by the common feature that the reaction is discontinued as soon as the desired degree of acetalization is reached. In this process it is frequently put up with the fact that the acetali2ation equilibrium has not yet been reached, i.e. the reaction is carried out with an excess amount of butyraldehyde and is discontinued prior to reaching the acetalization equilibrium.
The present inYention relates to a process for the preparaticn of polyvinylbutyral ha-ving improveà proper~
29 tiès and comprises sub~ecting a polyvinylbutvral having _ 4 _ HOE 77/F 140 a ViSCO~lty o~ frcm lO to 200 cp (measured according to DiN 53 015 ar a 5 ~ by weight s.lution in etnanol at 23C) and a content of from 17 to 24 ~ by weight of ~inyl alcohol units n an aqueous medium, at a temperatu~e of 50 to 70~C in the presence o~ from 0.01 t~,5 % by weight, - calculated on the polyvinylbutyral, of an organic sulfonic acid being e~ecti-~re as emulsifier and having from 8 to 30 carbon atoms to ar. after-treatment Ior 0.5 to 10 hours under acetalization conditions knot~l per se, and thereafter separating said poiyvinylbutyral as usual.
The polyvinylbutyral obtained according to the inven-tion is marked by a considerably increased strength and stiffness and at the same time shows a reduced solubility.
For the process Or the invention it is, in principle, insi~nificant according to ~rhich process the polyvinylbu-tyral employed has been prepared. ~lowever, since the after-treatment is effected in an aqueous phase, it is advanta~eou~ to use polyvi.nylbutyrals which have also been prepared in a~ aqueous ph~se. For this process it is particularly ad~antageous to effect the after-treatment immediately and without interruption following the acetalization, so that the acetalization and the after-treatment are carried out in a single operation without separating the acetalization liquor, and the reaction product is subse~uently separated in known manner.
However, also dry polyvinylbutyrai powder may be subjected to the a~ter-treatment o~ the in~ention.
The a~ter~treatment Ol a poly-~inylbutyral prepared in 29 an aqueous pha~e, in -~hose pleparatiorl the reaction tem ~ 5 ~ _ 7~F 140 perature nas ~e~ less than 20C up to the co~pletion o~
the acetallzation~ is particularly advantageous. This means that in this case the polyvinylbutyral is obtained in a grain size (particle diameter) which is less than 1 millimet2r for more than 90 %, for the most part even less than 0.5 millimeter, and which is therefore particularly suitable for the after-treatment. In the case of coarser polyvinylb~tyral particles it is recommended to grind the particles to the grain size indicated prior to the after-treatment.
The improvement of the mechanical properties dependsonly to a minor degree on the molecular weight of the polyvinylbutyral employed. It is therefore possible to subject polyvinylbutyrals of a range of molecu].ar weight which is as extensive as is interesting in practice to the after-treatlnent according to the invention. In this range there are generally polyvinylbutyrals having a viscosity of from 10 to 200 cp, preferably from 50 to 100 cp (measur-ed according to DIN 53 015 at a 5 % by wei~ht solution in ethanol at 23C).
Of special importance for the success of the process according to the invention is the chemical composition of the polyvinylbutyral. In principle, it is easier to im-prove the ~echanical properties in polyvinylbutyrals which have a high content of vinyl alcohol units than in those having a lo-.~ content of vinyl alcohol units. If the portion of vinyl alcohol units is les~ than 17 ~ by weight, a distinct improvement of the mechanical properties can no 29 longer be observed. If the portion is more than 24 ~ ~y 73 ~
- 6 - HOE 7'1/F 140 weightJ tn~ a~ter-Lreatment yields a polyvinylbutyral which can no longer be processed satisfactorily. This i5 why there is used a polyvinylbutyral having a content of from 17 ~o 24 ~ bv weight and preferably from 18 to 23 ~ by weight of vinyl alcohol units.
The mechanical properties of the reaction ~roduct are al50 strongly influenced by the temperature applied in the after-treatment. Temperatures of less ihan 50C are not recommended, since the reaction will take too long in this case. At a temperature of more than 65C, in the case of high molecular weight polyvinylbutyrals of more than 70C, the polymer shows a tendency to-:ard.s a larger grain size and lump f`ormation. The process is therefore oarried out generally at a temperature in the range of from 50 to 70~, preferably 50 to 65C.
The period of after-treatment is generally in the range of from 0.~ to 10 hours, preferably from 1 to 7 hours.
A particularly important requirement for improving the proper~ies of the polyvinylbutyral ~y the after-treat-ment according to the invention is the presence of from 0.01 to 0.5, preferably from 0.05 to 0.2 p by weight, cal-culated on the polyvinylbutyral, of an organic sulfonic acid having from 8 to 30 carbon atoms and bein~ effective as emulsifier. There are suitable for this purpose alkyl~
sulfonic acid~ and alkyiaryl-sulfonic acids, for example dodecylben~ene-sulfonic acid or he~adecane~sulfonic ac.id.
It is also ?ossible to use r.~i~tures of such acids. The 29 aliphatic radical of the sulfonic acifls may be br2nclled - 7 - HOF._77/F 140 and the aro~atic radical may a~so be substituted by one or several alkyl grou?s.
The after-treatment is generally carried out in an aqueous medium under usual acetalization conditions, while using from I to 100 parts by weight of water per part by weight of polymer and from about 0.1 to 5 % by weight of an inorganic acid, calculated on the aqueous medium. The reaction mixture is normally agitated by stirring. As inorganic acid there is used preferably sulfuric acid or hydrochloric acid. Further it is recommended, in order ro maintain the existing degree of acetalization in the poly-mer, to add n~butyraldehyde in an amount approxima-tely corresponding to the equilibrium concentration, for which purpose from 0.1 to 5 ~ by weight, calculated on the polymer, are sufficient, depending on the reaction condi-tions. The concentration of n-butyraldehyde is to be chosen in such a manner that the portion of vinyl alcohol units is in the range of from 17 to 2l~, prefcrably from 18 to 23 % by weight, also in the after-treated polymer.
2Q Due to the described addition ol an excess amount of inorganic acid it is not absolutely necessary t~ employ the organic sulfonic acid having an emulsifying effect as free acid. ~ather, use may be made also of any salts of these sulfonic acids, from which the free acid is formed in the raction mixture.
The after-treatment of the poly~inylbutyral accord-ing to the inventlon is completed by the separation of the final product. This proces$ i3 carried out ln the same 2~ manner as ~nown for the prepararion of pol-yvinyl~utyrals - 8 - HOE 77/F 1Ll0 from arl a~ue~us In~^iiurn. The ~orking-up consists in the complete remo~al of the acid from the polymer, preferably by a thorough washin~ with water. According to known methods it is recommendeA to apply a small amount of alkali onto the polymer Drior to the subsequent drying, so that from 5 to 100 ml of 0.01 normal HCl solution are requiredS for example, to neutralize 100 g of polyvinyl-butyral.
It is a special advantage of the process of the in-vention that the properties of the final pro-duct can be influenced gradually and in a reproducible manner by vary~
ing the individual process features. This is particularly important, since the structure of the polyvinylbutyral employed as starting material may be variable depending on the conditions of its prepar-tion. Polyvinylbutyrals which have been prepared, for example, at a low temperature, have a structure whi^h is as a rule more statistic than that of pol.yvinylbutyrals obtained at hi~;her temperatures. There-fore it is possible to obtain from the former throu~h an intensive after-treatment a final product of the same qua-lity as that of the latter products which are not modi-fied as strongly by the conditions of the after-treatment.
The manner in which the properties of the polyvinyl-butyral are influenced through a modification of the pro-~5 cess parameters during the after-treatment according to the invention can be ascertained without difficulty, for example, by determining the ~iscosity of a 5 % ethanolic so]ution at 23C aceording to DIN 53 015 and observing the 29 ~:iscosity change at this tem.?erature.
- 9 - H0~_77/F 140 For t~1ls ~ut~posc the polyvinylbutyral is dissolved at 70(. Sui)sequently the soluti.on is cooled wit.hin 5 minutes to the measuring temperature, and the viscosity is determir.ed immedi.ately. Following definite periods of time r for example after one hour, one day and~or one week each, the viscosity is again determined at 23C. Those polymers having ~ portion of vinyl alcohol units of less than 23 ~ by weight which have not been after-treated do practicaliy not sho~ any change of viscosity in this treatment. Polyvinylbutyrals which have been after--treated for only a short time show only a slight thickening in solution, whereas those polyvinylbutyrals which have been after-treated for several hours under more strict condi-tions, for example at a temperature of more than 65C and in the presence of more than 0.2 ~ by weight of alkane-sulfonic acid, may thicken in solution already within one hour.
In principle, it is also possible, however, to ob-serve the chang~ of the properties of the polyvinyl~utyral by measuring all the other properties that are altered by the after-treatment.
The property changes of the polyvinylbutyral obtain-ed by the process according to the invention are very con-spicuous. Especially the strength and the stiffness of the polymer are increased considerably. Plasticized sheets which are prepared from the polyvinylbutyral treated ac cor~in~Y to the inventioll show a stiffness that has been marked~y încreased, a stren~th that has been considera`nly 29 increased 2t a defined elongati.on, as well as an increaced ~ '7~
tensile strnngth with an elongation at tear only sli~htly reduced, as compared with known Doiyvinylbutyral sheets.
At a temperature Or less than 100C the sheets manufac-tured from the polyvinylbuty!al prepared according to the invention show a tendency to flowing that has been consi-derably reduced, which facilitates their use as oonding sheets for sa~ety glass. Further the after-treatment ac-cording to the invention surprisingly also strongly re-duces the undesired stickiness of the polyvinylbutyral sheets. When using polyvinylbutyral having an appropriate molecular weight distribution, the flow and the processing properties are in no way adversely affected as compared with known polyvinylbutyrals. In spite of the reduced solubility of the polyvinylbutyral in some solvents, which t5 ls caused by the after-treatment, said polyvinylbutyral is excellently compatible with common plasticizers and yields sheets having a high transparency.
The p.ocessing of the polyvinylbutyral obtained by thc after-treatment according to the invention into bond-ing sheets is carried out in usual manner. As the flowproperties in the plasticizer-containing melt are reduced by the after-treatment, it is recommended to employ poly-mers having a molecular weight - expressed by the viscosity in a 5 ~ ethanolic solution at 23C according to DIN
53 015 - which is generally lower than with the polyvinyl-butyrals commonly used for this purpose. In order to further i~prove the flow properties it is also possible to add polyvinylbutyrals having a lower molecular weight.
29 Finally, the proce3sing properties of the polyvinylbutyral 3~
prepared il7 accord-~nce with the invention may also be influenced '~y varying the plastici~er added.
The amount of plasticizer to be added is generally in the range of from 20 to 60 parts by .~eight, especially from 30 to 50 parts by weight for 100 parts by weight of polyvinylbutyral. As plasticizers there are used the compounds th~t are commonly employed, especially esters of polyhydric alcohols or of polybasic acids. There are suitable, for example, esters of triethylene-glycol with aliphatic carboxylic acids havj.ng from 6 to 10 carbon atoms, such as, in particular, 2-ethylbutyric acid, gly-cerol monooleate, dibutyl sebacate, di(B-butoxymethyl)-adipate, dioctylphthalate and tricresyl phosphate. These plasticizers may be used individually or combined.
Furthermore, there may be added a substance which makes the mixture stable to degr~dation, for example, a small ~mount of an alkali or a ~alt having an alkaline reaction, moreover, an oxidation stabilizer, such as a phenol, bisphenol or terpene phenol substituted in the 2,
4 and/or 6 positions.
Finally, the mixtures may also contain an additive which influences the adhesion of the sheets to one another or to glass, for example a salt of a carboxylic acid, a fluoride, lecithin or an alkylene urea.
The above-mertioned stabilizer as well as the addi-tive for influencing the adhesion are usually added in an amount of from 0.001 to 1 % by weight, calculated on the total mixture. The polyYinylbutyral, the plasticizer and 29 optiollally the additive are mixed in known manner by stir--7~
~ 12 - HOE 77~F 140 ri.ng tne co~ponents together at normal temperature and optionally leaving the mixture to stand, or by kneading or rolling at an elevated temperature or immediately in the processing stage on a calender or in an extruder.
The manufacture of glass compounds with the aid of bonding sheets containing polyvinylbutyral treated accord-ing to the invention may be effected according to conven-tional methods, for example by molding the sheet between two glass panes at a temperatures of from 120 to 160C and a pressure of from 5 to 20 bars. In the manufacture of such compounds above all the low stickiness ànd the reduc ed flow propertie3 of the sheets at temperatures of less than 100C are advantageous, which particularly facilitates the insertion of the sheets between bulged glass panes and also reduces the formation of air-bubbles in tl1e said com-pounds.
Moreover, the polyvinylbutyrals prepared according to the invention are also suitable for all other applica-tion purposes of polyvinylbutyral, for example as addi-tives to lacquers and primers.
The following Examples serve to illustrate the inven-tion.
E X A M P L E 1:
270 Grams of a polyvinylbutyral whose particle size `25 was less than 0.5 mm for 94 % and which had a content of vinyl alcohol unit.s of 20.0 % by weight, the 5 ~ ethanolic solution of which had ~ viscosity of 68 cp at 23C, were stirred in a rnixiure ol` 2,5~0 g of` water, 1 g of n-buty-29 raldehyde, 0.28 g of hexadecanè-sulfonic acid and 17n m.l 8~
of concentr2te(1 hydl ochloric acid for 5 hours at 60C.
For the working-up, the polymer was filtered off with suction, washed with water until neutral, stirred with 2 1 of water and 7 g of 10 g sodium hydroxide solution for
Finally, the mixtures may also contain an additive which influences the adhesion of the sheets to one another or to glass, for example a salt of a carboxylic acid, a fluoride, lecithin or an alkylene urea.
The above-mertioned stabilizer as well as the addi-tive for influencing the adhesion are usually added in an amount of from 0.001 to 1 % by weight, calculated on the total mixture. The polyYinylbutyral, the plasticizer and 29 optiollally the additive are mixed in known manner by stir--7~
~ 12 - HOE 77~F 140 ri.ng tne co~ponents together at normal temperature and optionally leaving the mixture to stand, or by kneading or rolling at an elevated temperature or immediately in the processing stage on a calender or in an extruder.
The manufacture of glass compounds with the aid of bonding sheets containing polyvinylbutyral treated accord-ing to the invention may be effected according to conven-tional methods, for example by molding the sheet between two glass panes at a temperatures of from 120 to 160C and a pressure of from 5 to 20 bars. In the manufacture of such compounds above all the low stickiness ànd the reduc ed flow propertie3 of the sheets at temperatures of less than 100C are advantageous, which particularly facilitates the insertion of the sheets between bulged glass panes and also reduces the formation of air-bubbles in tl1e said com-pounds.
Moreover, the polyvinylbutyrals prepared according to the invention are also suitable for all other applica-tion purposes of polyvinylbutyral, for example as addi-tives to lacquers and primers.
The following Examples serve to illustrate the inven-tion.
E X A M P L E 1:
270 Grams of a polyvinylbutyral whose particle size `25 was less than 0.5 mm for 94 % and which had a content of vinyl alcohol unit.s of 20.0 % by weight, the 5 ~ ethanolic solution of which had ~ viscosity of 68 cp at 23C, were stirred in a rnixiure ol` 2,5~0 g of` water, 1 g of n-buty-29 raldehyde, 0.28 g of hexadecanè-sulfonic acid and 17n m.l 8~
of concentr2te(1 hydl ochloric acid for 5 hours at 60C.
For the working-up, the polymer was filtered off with suction, washed with water until neutral, stirred with 2 1 of water and 7 g of 10 g sodium hydroxide solution for
5 hour at 60GC, then filtered off with suction and dried at 40C in ~Jacuo.
Subsequently the polymer was mixed with 29 ~ by weight of tri ei;hylene-glycol-bis(2-ethylbutyric acid ester) and extruded at 170C. Sheets having a thickness 10 of` 0.8 mm were molded f`rom the extruded product. The following Table shows some properties of these sheets as compared with sheets manufactured from the untreated starting polymer.
polyrner portion of;nelt-flow index ultimate elongation strength at vinyl al-i1o150C /i2o60C tensile at break elongatiollor cohol st;rength 100 g units(g/10 min)/(mg/h) ~N/cm2) (N/cm2) (% b. wt.~
_ ~ .. _ ~ __ urtreated 20.0 4.62 / 134 2250 325 160 (Crimson) treated 20.4 0.82 ~ O 2750 300 450 determination according to DIN 53 735 at 150C under a load of` 10 kg determination of the output in mg~h at 60C under a load of 21.6 kg, apparatus as in i1o150C
***
deter.rnination according to DIN 53 455 after condi-tioning a. 23C and a relative air humidity of 50 %, witl1 a tension rate of ~0 cm/m~in, a clarr.pin~ length of 50 mm, and a width of the measuring tape of 15 rnm.
'7~
- 14 - _E 77/F 140 E X A ~1~'L' ' ~ ?~ ~
As descrlbed in E~ample 1, a fine-grained polyvi.nyl-butyral having a portion of vinyl alcohol units of 19.5 %
by wei~ht, the 5 ~ ethar.olic solution of ~hich had a vis-cosity of 64 cp at 23C, was stlrred in 10 times the amountof water for 3 hours at 62C. The aqueous mixture contain-ed 2 p of sulfuric acid and 0.1 g of n-butyraldehyde.
Further, 0.2 p (calculated on the polymer) of a sodium salt of r13-C18-alkane-sulfonic acids was added to the re-act.ion mixture. After this treatment 'he polymer was worked up 2S indicated in Example 1 and extruded into a slleet containing a plasticizer.
The property changes of the polymer are shown by the following Tabl~.
po]ymer portion of melt-flow index ultimate blocking vinyl al- ilo150C~i2o60C tensile (sec) cohol strength nits (g/lO min)/(mg/h) (N/cm2) (~ ~. wt.) , _ _ _ . _ .
untreated 19.5 7.15 / 175 1,900 7,000 ( compa-rison) = - 20.7 2.00 / 0 2,800 1,200 cf. Example 1 **
The determination of the sheet adhesion which is termed "blockir.g" in the Table was effected as follo~s:
Stripe of plastic shee~ of 15x100 mm having a def'ini-tely ro~ghened surface~ were put on top of one another at a le.ngth of' 5 cm a.ter corditioning at 23~C ard - 15 - ~OE 77~F 140 at a re.ati~-e air humidity of 50-%, and then charged with a loacl of lN/cm . Subsequently the said strips were hung up under normal climatic conditions and pulled aF,art with a weight of 200 g. The period until the strips of sheet separated from one another was determined in seconds.
According to known methods, giass compounds having a high impact strength and an excellent t.ransparency could be made from sheets produced from the polymer thus treated.
E X A M P L R 3:
100 Parts each of a polyvinylbutyral having a 93 % por-tion of particles whose diameter was less than 1 mm and having a content of vinyl alcohol units of 21.5 % by weight were stirred in a mixture of 900 parts of 2.5 ~
hydrochloric acid, 2 parts of n-butyraldehyde and 0.2 part of dodecylbenzene-sulfonic acid f`or 6 hours each time at the temperatures indicated in thls Table below and were then worked up as described in Example 1.
Of the polymers whose granular structure has remain~
ed unchan~ed, 5 ~ solutions in ethanol were prepared each time at 70C. After cooling to 23C, the viscosity of the solutions was determined according to DIN 53 015. The results are shown in the following Table.
7~34 .~
treatment I ~iscosity, 5 % .in et;hanol at 23C (cp) tempera~ure after 5 minutes after 24 hours (C) ~ ---~
.. ... . . . _ . _~
Subsequently the polymer was mixed with 29 ~ by weight of tri ei;hylene-glycol-bis(2-ethylbutyric acid ester) and extruded at 170C. Sheets having a thickness 10 of` 0.8 mm were molded f`rom the extruded product. The following Table shows some properties of these sheets as compared with sheets manufactured from the untreated starting polymer.
polyrner portion of;nelt-flow index ultimate elongation strength at vinyl al-i1o150C /i2o60C tensile at break elongatiollor cohol st;rength 100 g units(g/10 min)/(mg/h) ~N/cm2) (N/cm2) (% b. wt.~
_ ~ .. _ ~ __ urtreated 20.0 4.62 / 134 2250 325 160 (Crimson) treated 20.4 0.82 ~ O 2750 300 450 determination according to DIN 53 735 at 150C under a load of` 10 kg determination of the output in mg~h at 60C under a load of 21.6 kg, apparatus as in i1o150C
***
deter.rnination according to DIN 53 455 after condi-tioning a. 23C and a relative air humidity of 50 %, witl1 a tension rate of ~0 cm/m~in, a clarr.pin~ length of 50 mm, and a width of the measuring tape of 15 rnm.
'7~
- 14 - _E 77/F 140 E X A ~1~'L' ' ~ ?~ ~
As descrlbed in E~ample 1, a fine-grained polyvi.nyl-butyral having a portion of vinyl alcohol units of 19.5 %
by wei~ht, the 5 ~ ethar.olic solution of ~hich had a vis-cosity of 64 cp at 23C, was stlrred in 10 times the amountof water for 3 hours at 62C. The aqueous mixture contain-ed 2 p of sulfuric acid and 0.1 g of n-butyraldehyde.
Further, 0.2 p (calculated on the polymer) of a sodium salt of r13-C18-alkane-sulfonic acids was added to the re-act.ion mixture. After this treatment 'he polymer was worked up 2S indicated in Example 1 and extruded into a slleet containing a plasticizer.
The property changes of the polymer are shown by the following Tabl~.
po]ymer portion of melt-flow index ultimate blocking vinyl al- ilo150C~i2o60C tensile (sec) cohol strength nits (g/lO min)/(mg/h) (N/cm2) (~ ~. wt.) , _ _ _ . _ .
untreated 19.5 7.15 / 175 1,900 7,000 ( compa-rison) = - 20.7 2.00 / 0 2,800 1,200 cf. Example 1 **
The determination of the sheet adhesion which is termed "blockir.g" in the Table was effected as follo~s:
Stripe of plastic shee~ of 15x100 mm having a def'ini-tely ro~ghened surface~ were put on top of one another at a le.ngth of' 5 cm a.ter corditioning at 23~C ard - 15 - ~OE 77~F 140 at a re.ati~-e air humidity of 50-%, and then charged with a loacl of lN/cm . Subsequently the said strips were hung up under normal climatic conditions and pulled aF,art with a weight of 200 g. The period until the strips of sheet separated from one another was determined in seconds.
According to known methods, giass compounds having a high impact strength and an excellent t.ransparency could be made from sheets produced from the polymer thus treated.
E X A M P L R 3:
100 Parts each of a polyvinylbutyral having a 93 % por-tion of particles whose diameter was less than 1 mm and having a content of vinyl alcohol units of 21.5 % by weight were stirred in a mixture of 900 parts of 2.5 ~
hydrochloric acid, 2 parts of n-butyraldehyde and 0.2 part of dodecylbenzene-sulfonic acid f`or 6 hours each time at the temperatures indicated in thls Table below and were then worked up as described in Example 1.
Of the polymers whose granular structure has remain~
ed unchan~ed, 5 ~ solutions in ethanol were prepared each time at 70C. After cooling to 23C, the viscosity of the solutions was determined according to DIN 53 015. The results are shown in the following Table.
7~34 .~
treatment I ~iscosity, 5 % .in et;hanol at 23C (cp) tempera~ure after 5 minutes after 24 hours (C) ~ ---~
.. ... . . . _ . _~
6~ 98 . ._ . . _ As compared with the above polymer compositions~ the solution of the untreated polymer had a viscosity of 55 cp 5 minutes after cooling znd of 56 cp 24 hours after cool-ing.
E X A M P L E 4:
. . _ _ _ A polymer having the properties indicated in the fol-lowing Table was treated as described in Example 3, with the difference that 0.4 % by weight of dodecylbenzene-sul-fonic acid was present ~calculated on the polymer). The reaction temperature was 65C. The worlcing-up was effect-ed as descrlbed in Example l.
polymer portion of viscosity, 5 ~ in ethanol at 23C melt-fl~J
vinyl al- after 5 min after 24 hours index (with-cohol (cp) out plasti-units cizer (~ by i10190C
weight) (g/10 min)) _. _ _ _.... . . __ . .
~treated 22.5 24 24 more ~han (compari- 50 treated 22.7 215 more than 5.2 _ _ _ 15,000 ~
_ ~
not measurablel~re pnecisely ~ 17 - HOE 77~F 1L!O
E X A 1 ~ L ,r 1,000 Parts of a 10 ~ solution of polyvinyl alco-hol Spolymerization degree about 1,200) were reacted in known manner 'n the presence of 65 parts of concentrated hydrochloric acid at 15C with n-butyraldehyde. 15 Parts of butyraldehyde were introduced at first, while stirring9 and subsequently another 42 parts of butyraldehyde were added within 10 minutes. In the course Or this process the polyvinylbutyral being formed precipitated in a fine-grained form. The mixture was then heated, while stirring, to 40C at a rate of 15C per hour and was maintained for 4 hours at this temperature. Subsequently the mixture was divided. One ha:lf was worked up according to the method described in Example 1 (comparison test).
The other half Or the mixture was mixed with 0.15 part of C13-C18-alkane--sulfonic acids in 5 parts of water and heated to 62C within 10 minutes. After 1, 3 and 5 hours of reacti.ng at 62C each time, samples were taken, and after 7 hours the reaction was discontinued. All samples and the remainder of the reaction mixture were worked up as in Example 1.
Several properties of the polymers ha~e been summa-rized in the following Table.
- l& - HOE 7'7/F 140 ~ ~* ~o~ I ~o ~* ~*
.C ~ g~ ~ E ~,_ .- ~ '.D ~ s~
W E~ ~ :~t ~ N ~\I .,~ "
C o __ ~ E
o ~ ** s~ ~ ~
~ c~ .,, ~ 8 ' ,, ~ C) o o o o o ~.
~ ~d O O~OD ~ -c~ ~
~ ~ Xo~ ~ _ ~
o ~ ~ o ~ ~ =~
~ ~ ~ Ln o ~ u~ ^ a ~_ ~ . I O ~ ~ ~ ~ O E ~
0~ ~ _ ~X ~
0 3 ~ Ln c~ o ~ ~\1 0 ~ X C~ , :~ ~ .~ ..
~ .
:~ u~ ~ ~ co 3. ~.
.~ ~
_ Go ~ ~
~O ~ ~I C~
So~ ~ ~c~ Q ~ ~ ~ 2 Q ~ c ~
O E ~
.~ ~ ~ ~
~ . ~ ~ .~ H -~ 0 O
~ ~ o (~ U~ ~ J~
.` .,'`. ~ ~ X**x E X A ~I P L E 6:
A polymer prepared according to the state of the art as indicated in Example 5, which had a portion of vinyl alcohol units of 19.7 % by weight and a grain size of less than 0.5 mm foT 96 %, the viscosity of the 5 %
ethanolic solution being 81 cp, was stirred each time in ~he presence of g times the amount of 1.8 % hydrochloric acid and in the presence of 2.5 %, calculated on the polymer, of n-butyraldehyde for 7 hours at 55C. The amount of dodecyl-benzene-sulfonic acid indicated in the following Table was added each time to the corresponding batches. The change of some properties is shown in said Table as compared with the untreated starting product.
polymer addition of dode portion of properties of a 0.76 mm cyl-benzene-sulf- vinyl alco- sheet (29 % of plastici-onic aci~ hol units zer content*) (%, calculated ~% b. wt.) melt-flow strength at an on the polymer) index elongation of 206 C lO0 % ~Example l) (mg/hour) (N/cm ) untreated _ 19.7 175 150 (comparison) treated 0.05 19.5 10 280 treated 0.1 19.7 4 320 treated 0.3 19.3 0 350 , _ * triethylene-glycol-bis(2-ethylbutyric acid ester)
E X A M P L E 4:
. . _ _ _ A polymer having the properties indicated in the fol-lowing Table was treated as described in Example 3, with the difference that 0.4 % by weight of dodecylbenzene-sul-fonic acid was present ~calculated on the polymer). The reaction temperature was 65C. The worlcing-up was effect-ed as descrlbed in Example l.
polymer portion of viscosity, 5 ~ in ethanol at 23C melt-fl~J
vinyl al- after 5 min after 24 hours index (with-cohol (cp) out plasti-units cizer (~ by i10190C
weight) (g/10 min)) _. _ _ _.... . . __ . .
~treated 22.5 24 24 more ~han (compari- 50 treated 22.7 215 more than 5.2 _ _ _ 15,000 ~
_ ~
not measurablel~re pnecisely ~ 17 - HOE 77~F 1L!O
E X A 1 ~ L ,r 1,000 Parts of a 10 ~ solution of polyvinyl alco-hol Spolymerization degree about 1,200) were reacted in known manner 'n the presence of 65 parts of concentrated hydrochloric acid at 15C with n-butyraldehyde. 15 Parts of butyraldehyde were introduced at first, while stirring9 and subsequently another 42 parts of butyraldehyde were added within 10 minutes. In the course Or this process the polyvinylbutyral being formed precipitated in a fine-grained form. The mixture was then heated, while stirring, to 40C at a rate of 15C per hour and was maintained for 4 hours at this temperature. Subsequently the mixture was divided. One ha:lf was worked up according to the method described in Example 1 (comparison test).
The other half Or the mixture was mixed with 0.15 part of C13-C18-alkane--sulfonic acids in 5 parts of water and heated to 62C within 10 minutes. After 1, 3 and 5 hours of reacti.ng at 62C each time, samples were taken, and after 7 hours the reaction was discontinued. All samples and the remainder of the reaction mixture were worked up as in Example 1.
Several properties of the polymers ha~e been summa-rized in the following Table.
- l& - HOE 7'7/F 140 ~ ~* ~o~ I ~o ~* ~*
.C ~ g~ ~ E ~,_ .- ~ '.D ~ s~
W E~ ~ :~t ~ N ~\I .,~ "
C o __ ~ E
o ~ ** s~ ~ ~
~ c~ .,, ~ 8 ' ,, ~ C) o o o o o ~.
~ ~d O O~OD ~ -c~ ~
~ ~ Xo~ ~ _ ~
o ~ ~ o ~ ~ =~
~ ~ ~ Ln o ~ u~ ^ a ~_ ~ . I O ~ ~ ~ ~ O E ~
0~ ~ _ ~X ~
0 3 ~ Ln c~ o ~ ~\1 0 ~ X C~ , :~ ~ .~ ..
~ .
:~ u~ ~ ~ co 3. ~.
.~ ~
_ Go ~ ~
~O ~ ~I C~
So~ ~ ~c~ Q ~ ~ ~ 2 Q ~ c ~
O E ~
.~ ~ ~ ~
~ . ~ ~ .~ H -~ 0 O
~ ~ o (~ U~ ~ J~
.` .,'`. ~ ~ X**x E X A ~I P L E 6:
A polymer prepared according to the state of the art as indicated in Example 5, which had a portion of vinyl alcohol units of 19.7 % by weight and a grain size of less than 0.5 mm foT 96 %, the viscosity of the 5 %
ethanolic solution being 81 cp, was stirred each time in ~he presence of g times the amount of 1.8 % hydrochloric acid and in the presence of 2.5 %, calculated on the polymer, of n-butyraldehyde for 7 hours at 55C. The amount of dodecyl-benzene-sulfonic acid indicated in the following Table was added each time to the corresponding batches. The change of some properties is shown in said Table as compared with the untreated starting product.
polymer addition of dode portion of properties of a 0.76 mm cyl-benzene-sulf- vinyl alco- sheet (29 % of plastici-onic aci~ hol units zer content*) (%, calculated ~% b. wt.) melt-flow strength at an on the polymer) index elongation of 206 C lO0 % ~Example l) (mg/hour) (N/cm ) untreated _ 19.7 175 150 (comparison) treated 0.05 19.5 10 280 treated 0.1 19.7 4 320 treated 0.3 19.3 0 350 , _ * triethylene-glycol-bis(2-ethylbutyric acid ester)
7~a E X A M P L E 7:
_ _ _ In a manner analogous to that described in Example 5, various polyvinylbutyrals were prepared and after-treated in a single operation by way of the process according to the invention.
1,250 Parts each of a 8 ~ solution of polyvinyl alco-hol were cooled together with 85 parts of concentrated hydrochloric acid and 15 parts of n-butyraldehyde to 13C.
The mixtures contained 0.3 part of octadecane-sulfonic acid. Subsequently 40, 44 and 48 parts, respectively, of n-butyraldehyde were added dropwise within 30 minutes at 13C to three different batches. Thereafter the batches were heated to 63C within 2 hours at a constant rate and were maintained for 5 hours at this temperature. Already when reaching a temperature of 55C, the desired range of the acetalizationn degree was reached. In the case of one of the batches, a sample was tak~n at this point, which sample showed the properties of a polymer according to the state of the art, as was to be expected.
In contradistinction thereto, an intensification of the intermolecular forces was found in the polymers which had been treated for a prolonged period of time according to the invention, as shown by the following Table.
7~
polymer portion of viscosity, 5 % in ethanol, 23C properties of a 0.76 ~n vinyl alco- after S min after 24 hours sheet (29 % of plasti-hol units (cp) (cp) cizer content*) (% b. wt.) tensile blocking strength ~N/cm2) (sec) 1 after- 18.9 53 62 2500 1800 treated 2 after- 20.2 61 91 2750 900 treated 2 com- 19.2 52 52 21007500 parison 3 after- 22.2 69 109 2800 420 treated * triethylene-glycol-bist2-ethylbutyric acid ester) ~ .
_ _ _ In a manner analogous to that described in Example 5, various polyvinylbutyrals were prepared and after-treated in a single operation by way of the process according to the invention.
1,250 Parts each of a 8 ~ solution of polyvinyl alco-hol were cooled together with 85 parts of concentrated hydrochloric acid and 15 parts of n-butyraldehyde to 13C.
The mixtures contained 0.3 part of octadecane-sulfonic acid. Subsequently 40, 44 and 48 parts, respectively, of n-butyraldehyde were added dropwise within 30 minutes at 13C to three different batches. Thereafter the batches were heated to 63C within 2 hours at a constant rate and were maintained for 5 hours at this temperature. Already when reaching a temperature of 55C, the desired range of the acetalizationn degree was reached. In the case of one of the batches, a sample was tak~n at this point, which sample showed the properties of a polymer according to the state of the art, as was to be expected.
In contradistinction thereto, an intensification of the intermolecular forces was found in the polymers which had been treated for a prolonged period of time according to the invention, as shown by the following Table.
7~
polymer portion of viscosity, 5 % in ethanol, 23C properties of a 0.76 ~n vinyl alco- after S min after 24 hours sheet (29 % of plasti-hol units (cp) (cp) cizer content*) (% b. wt.) tensile blocking strength ~N/cm2) (sec) 1 after- 18.9 53 62 2500 1800 treated 2 after- 20.2 61 91 2750 900 treated 2 com- 19.2 52 52 21007500 parison 3 after- 22.2 69 109 2800 420 treated * triethylene-glycol-bist2-ethylbutyric acid ester) ~ .
Claims (7)
1. Process for the preparation of a polyvinylbutyral hav-ing improved properties, which comprises subjecting 2 polyvinylbutyral having a viscosity of from 10 to 200 cp (measured according to DIN 53 015 at a 5 % by weight solution in ethanol at 23°C) and a content of from 17 to 24 % by weight of vinyl alcohol units in an aqueous medium, at a temperature of from 50 to 70°C in the presence of from 0.01 to 0.5 % by weight, calculated on the polyvinylbutyral, of an organic sulfonic acid having from 8 to 30 carbon atoms and being effective as emulsifier to an after-treatment for a period of from 0.5 to 10 hours under acetalization conditions known per se and thereafter separating said polyvinyl-butyral. as usual.
2. Process as claimed in claim 1, which comprises using a polyvinylbutyral having a viscosity of from 50 to 100 cp (measured according to DIN 53 015 at a 5 % by weight solution in ethanol at 23°C).
3. Process as claimed in claim 1, which comprises using a polyvinylbutyral having a content of from 18 to 23 %
by weight of vinyl alcohol units.
by weight of vinyl alcohol units.
4. Process as claimed in claim 1, which comprises heat-ing the polyvinylbutyral in an aqueous medium to 50 to 65°C.
5. Process as claimed in claim 1, which comprises sub-jecting the polyvinylbutyral to an after-treatment for a period of from 1 to 7 hours.
6. Process as claimed in claim 1, which comprises using the organic sulfonic acid in an amount of from 0.05 to 0.2 % by weight, calculated on the polyvinylbutyral.
7. Process as claimed in claim 1, which comprises sub-jecting the polyvinylbutyral immediately after its preparation without separation from the acetalization liquor to an after-treatment in the same aqueous reac-tion medium and separating the polymer subsequently as usual.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2732717.9 | 1977-07-20 | ||
| DE2732717A DE2732717C3 (en) | 1977-07-20 | 1977-07-20 | Process for the production of polyvinyl butyral with improved properties |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1116784A true CA1116784A (en) | 1982-01-19 |
Family
ID=6014354
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000307711A Expired CA1116784A (en) | 1977-07-20 | 1978-07-19 | Process for the preparation of polyvinylbutyral having improved properties |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US4205146A (en) |
| EP (1) | EP0000699B1 (en) |
| JP (1) | JPS5422489A (en) |
| AR (1) | AR224502A1 (en) |
| AT (1) | AT366703B (en) |
| AU (1) | AU518178B2 (en) |
| BR (1) | BR7804657A (en) |
| CA (1) | CA1116784A (en) |
| DE (2) | DE2732717C3 (en) |
| IN (1) | IN150149B (en) |
| IT (1) | IT1097877B (en) |
| MX (1) | MX149297A (en) |
| ZA (1) | ZA784100B (en) |
Families Citing this family (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2401941A1 (en) * | 1977-08-31 | 1979-03-30 | Saint Gobain | PROCESS FOR MANUFACTURING POLYVINYL BUTYRAL AND POLYVINYL BUTYRAL OBTAINED BY THIS PROCESS |
| DE2846837A1 (en) * | 1978-10-27 | 1980-05-08 | Hoechst Ag | POLYVINYLBUTYRAL FILM |
| JPS5692142A (en) * | 1979-12-24 | 1981-07-25 | Sekisui Chem Co Ltd | Interlayer for laminated glass |
| US4452935A (en) * | 1981-06-01 | 1984-06-05 | Sekisui Kagaku Kogyo Kabushiki Kaisha | Interlayer film for laminated glass |
| JPS5832044A (en) * | 1981-08-14 | 1983-02-24 | Sekisui Chem Co Ltd | Laminated body used as an intermediate layer for laminated glass |
| JPS57200250A (en) * | 1981-06-01 | 1982-12-08 | Sekisui Chem Co Ltd | Interlay film for sandwich galss |
| FR2522003A1 (en) * | 1982-02-23 | 1983-08-26 | Saint Gobain Vitrage | PROCESS FOR THE PREPARATION OF POLYVINYLBUTYRAL |
| DE3246605A1 (en) * | 1982-12-16 | 1984-06-20 | Hoechst Ag, 6230 Frankfurt | FINE-PART POLYVINYL ACETALS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR COATING COATINGS |
| DE3303111A1 (en) * | 1983-01-31 | 1984-08-02 | Hoechst Ag, 6230 Frankfurt | THERMOPLASTIC MOLDS FROM SOFTENER-CONTAINING POLYVINYLBUTYRAL |
| DE3303156A1 (en) * | 1983-01-31 | 1984-08-02 | Hoechst Ag, 6230 Frankfurt | SOFTENER-BASED POLYVINYLBUTYRAL FILMS WITH REDUCED ADHESIVITY TO GLASS |
| FR2547589B1 (en) * | 1983-06-14 | 1986-03-21 | Saint Gobain Vitrage | PROCESS FOR PRODUCING POLYVINYLBUTYRAL AND PRODUCTS OBTAINED |
| DE3417653A1 (en) * | 1984-05-12 | 1985-11-14 | Hoechst Ag, 6230 Frankfurt | SOFTENER-CONTAINING THERMOPLASTIC POLYVINYLBUTYRAL MOLDINGS WITH REDUCED ADHESIVITY TO GLASS |
| US5349014A (en) * | 1984-08-02 | 1994-09-20 | E. I. Du Pont De Nemours And Company | Process for the production of polyvinyl butyral having improved properties |
| DE3429440A1 (en) * | 1984-08-10 | 1986-02-20 | Hoechst Ag, 6230 Frankfurt | POLYVINYLBUTYRAL WITH REDUCED STICKNESS AND IMPROVED TENSILE STRENGTH |
| DE3429441A1 (en) * | 1984-08-10 | 1986-02-20 | Hoechst Ag, 6230 Frankfurt | THERMOPLASTIC, SOFTENER-CONTAINING POLYVINYLBUTYRAL MOLDINGS |
| CA1276744C (en) * | 1985-07-02 | 1990-11-20 | George Etienne Cartier | Cross-linked polyvinyl butyral |
| JPH0347511Y2 (en) * | 1988-04-13 | 1991-10-09 | ||
| DE3835840A1 (en) * | 1988-10-21 | 1990-05-31 | Hoechst Ag | GRAY POLYMERISATES CONTAINING POLYVINYL ACETAL GROUPS ON POLYURETHANE GRAIN BASES, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| US4999253A (en) * | 1988-11-07 | 1991-03-12 | Monsanto Company | Polyvinyl butyral sheet |
| FR2648139A1 (en) * | 1989-06-08 | 1990-12-14 | Saint Gobain Vitrage | PROCESS FOR PRODUCING POLYVINYLBUTYRAL AND PRODUCTS OBTAINED |
| US5238994A (en) * | 1991-09-09 | 1993-08-24 | Monsanto Company | Forming polyvinyl butyral |
| US5332774A (en) * | 1992-10-16 | 1994-07-26 | Arco Chemical Technology, L.P. | Polyvinyl acetal resins based on hydroxyaldehydes and use of the resins in laminar structures |
| DE4323897A1 (en) * | 1993-07-16 | 1995-01-19 | Hoechst Ag | Plasticized molded polymer articles made from modified polyvinyl butyrals |
| JP2629575B2 (en) * | 1993-08-31 | 1997-07-09 | 日本電気株式会社 | Portable wireless communication device |
| CA2494510A1 (en) | 2002-08-02 | 2004-02-12 | E.I. Du Pont De Nemours And Company | A process for controlling polyvinylbutyral physical properties by controlling stereochemistry of same |
| DE10242417A1 (en) * | 2002-09-12 | 2004-03-25 | Wacker Polymer Systems Gmbh & Co. Kg | Process for preparation of polyvinyl acetals by aldehyde acetalization useful in production of safety glass for automobiles and in architecture, corrosion protection coatings, as a paint binder, and especially in printing inks |
| DE102004043907A1 (en) * | 2004-09-10 | 2006-03-16 | Kuraray Specialities Europe Gmbh | Plasticizer-containing PVB films with ether bonds containing carboxylic acid esters as co-plasticizer |
| US10676578B1 (en) * | 2019-05-10 | 2020-06-09 | Chang Chun Petrochemical Co., Ltd. | Interlayer film and laminated glass comprising the same |
| WO2023076440A1 (en) * | 2021-10-28 | 2023-05-04 | Solutia Inc. | Recovering poly(vinyl butyral) polymer |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB873263A (en) * | 1959-08-28 | 1961-07-19 | Seikisui Chemical Co Ltd | Process for preparing condensation products of polyvinyl alcohol and carbonyl compounds |
| DE1247663C2 (en) * | 1961-02-24 | 1975-11-27 | E.I. Du Pont De Nemours And Company, Wilmington, Del. (V.St.A.) | METHOD FOR MANUFACTURING POLYVINYL ACETALS |
| DE1545141A1 (en) * | 1962-08-13 | 1970-03-19 | Buna Chem Werke Veb | Process for the production of polyvinyl butyral |
-
1977
- 1977-07-20 DE DE2732717A patent/DE2732717C3/en not_active Expired
-
1978
- 1978-07-07 EP EP78100324A patent/EP0000699B1/en not_active Expired
- 1978-07-07 DE DE7878100324T patent/DE2860933D1/en not_active Expired
- 1978-07-13 IN IN772/CAL/78A patent/IN150149B/en unknown
- 1978-07-18 AR AR272996A patent/AR224502A1/en active
- 1978-07-18 US US05/925,873 patent/US4205146A/en not_active Expired - Lifetime
- 1978-07-18 AT AT0518778A patent/AT366703B/en not_active IP Right Cessation
- 1978-07-18 IT IT25850/78A patent/IT1097877B/en active
- 1978-07-19 ZA ZA00784100A patent/ZA784100B/en unknown
- 1978-07-19 JP JP8722678A patent/JPS5422489A/en active Granted
- 1978-07-19 AU AU38155/78A patent/AU518178B2/en not_active Expired
- 1978-07-19 CA CA000307711A patent/CA1116784A/en not_active Expired
- 1978-07-19 BR BR7804657A patent/BR7804657A/en unknown
- 1978-07-20 MX MX174243A patent/MX149297A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE2860933D1 (en) | 1981-11-12 |
| IT7825850A0 (en) | 1978-07-18 |
| AU3815578A (en) | 1980-01-24 |
| DE2732717A1 (en) | 1979-02-08 |
| AT366703B (en) | 1982-05-10 |
| JPS5422489A (en) | 1979-02-20 |
| EP0000699B1 (en) | 1981-08-12 |
| IN150149B (en) | 1982-07-31 |
| AU518178B2 (en) | 1981-09-17 |
| AR224502A1 (en) | 1981-12-15 |
| DE2732717C3 (en) | 1980-06-04 |
| BR7804657A (en) | 1979-03-20 |
| ATA518778A (en) | 1981-09-15 |
| DE2732717B2 (en) | 1979-09-20 |
| IT1097877B (en) | 1985-08-31 |
| EP0000699A1 (en) | 1979-02-21 |
| US4205146A (en) | 1980-05-27 |
| ZA784100B (en) | 1979-08-29 |
| JPS5728482B2 (en) | 1982-06-17 |
| MX149297A (en) | 1983-10-11 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |